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Chapter 2: Water
WHY DO WE NEED TO
DO THIS AGAIN!!!
• Very polar
• Oxygen is highly electronegative
• H-bond donor and acceptor
• High b.p., m.p., heat of vaporization,
surface tension
Properties of water
Chapter 2 - Properties of Water/pH/Buffers (slideshare)
Water dissolves polar
compounds
solvation shell
or
hydration shell
Non-polar substances are insoluble in water
Many lipids are amphipathic
How detergents work?
Hydrogen Bonding of Water
Crystal lattice of ice
One H2O molecule can
associate with 4
other H20 molecules
•Ice: 4 H-bonds per water
molecule
•Water: 2.3 H-bonds per water
molecule
Biological
Hydrogen
Bonds
Chapter 2 - Properties of Water/pH/Buffers (slideshare)
non-covalent interactions
Relative Bond Strengths
Bond type kJ/mole
H3C-CH3 88
H-H 104
Ionic 40 to 200
H-bond 2 - 20
Hydrophobic interaction 3 -10
van der Waals 0.4 - 4
Ionization of Water
Ionization of Water
H20 + H20 H3O+
+ OH-
Keq= [H+
] [OH-
]
[H2O]
H20 H+
+ OH-
Keq=1.8 X 10-16
M
[H2O] = 55.5 M
[H2O] Keq = [H+
] [OH-
]
(1.8 X 10-16
M)(55.5 M ) = [H+
] [OH-
]
1.0 X 10-14
M2
= [H+
] [OH-
] = Kw
If [H+
]=[OH-
] then [H+
] = 1.0 X 10-7
pH Scale
 Devised by Sorenson (1902)
 [H+] can range from 1M and
1 X 10-14
M
 using a log scale simplifies
notation
 pH = -log [H+
]
Neutral pH = 7.0
Weak Acids and Bases Equilibria
•Strong acids / bases – disassociate completely
•Weak acids / bases – disassociate only partially
•Enzyme activity sensitive to pH
• weak acid/bases play important role in
protein structure/function
Acid/conjugate base pairs
HA + H2O A-
+ H3O+
HA A-
+ H+
HA = acid ( donates H+
)(Bronstad Acid)
A-
= Conjugate base (accepts H+
)(Bronstad Base)
Ka = [H+
][A-
]
[HA]
Ka & pKa value describe tendency to
loose H+
large Ka = stronger acid
small Ka = weaker acid
pKa = - log Ka
pKa values determined by titration
Phosphate has three
ionizable H+
and three pKas
Buffers
• Buffers are aqueous systems that resist
changes in pH when small amounts of a strong
acid or base are added.
• A buffered system consist of a weak acid and
its conjugate base.
• The most effective buffering occurs at the
region of minimum slope on a titration curve
(i.e. around the pKa).
• Buffers are effective at pHs that are within
+/-1 pH unit of the pKa
Henderson-Hasselbach Equation
1) Ka = [H+
][A-
]
[HA]
2) [H+
] = Ka [HA]
[A-
]
3) -log[H+
] = -log Ka -log [HA]
[A-
]
4) -log[H+
] = -log Ka +log [A-
]
[HA]
5) pH = pKa +log [A-
]
[HA]
HA = weak acid
A-
= Conjugate base
* H-H equation describes
the relationship between
pH, pKa and buffer
concentration
Case where 10% acetate ion 90%
acetic acid
• pH = pKa + log10
[0.1 ]
¯¯¯¯¯¯¯¯¯¯
[0.9]
• pH = 4.76 + (-0.95)
• pH = 3.81
• pH = pKa + log10
[0.5 ]
¯¯¯¯¯¯¯¯¯¯
[0.5]
• pH = 4.76 + 0
• pH = 4.76 = pKa
Case where 50% acetate ion 50% acetic acid
• pH = pKa + log10
[0.9 ]
¯¯¯¯¯¯¯¯¯¯
[0.1]
• pH = 4.76 + 0.95
• pH = 5.71
Case where 90% acetate ion 10% acetic acid
• pH = pKa + log10
[0.99 ]
¯¯¯¯¯¯¯¯¯¯
[0.01]
• pH = 4.76 + 2.00
• pH = 6.76
• pH = pKa + log10
[0.01 ]
¯¯¯¯¯¯¯¯¯
[0.99]
• pH = 4.76 - 2.00
• pH = 2.76
Cases when buffering fails
Chapter 2 - Properties of Water/pH/Buffers (slideshare)

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Chapter 2 - Properties of Water/pH/Buffers (slideshare)

  • 2. WHY DO WE NEED TO DO THIS AGAIN!!!
  • 3. • Very polar • Oxygen is highly electronegative • H-bond donor and acceptor • High b.p., m.p., heat of vaporization, surface tension Properties of water
  • 5. Water dissolves polar compounds solvation shell or hydration shell
  • 6. Non-polar substances are insoluble in water Many lipids are amphipathic
  • 8. Hydrogen Bonding of Water Crystal lattice of ice One H2O molecule can associate with 4 other H20 molecules •Ice: 4 H-bonds per water molecule •Water: 2.3 H-bonds per water molecule
  • 12. Relative Bond Strengths Bond type kJ/mole H3C-CH3 88 H-H 104 Ionic 40 to 200 H-bond 2 - 20 Hydrophobic interaction 3 -10 van der Waals 0.4 - 4
  • 14. Ionization of Water H20 + H20 H3O+ + OH- Keq= [H+ ] [OH- ] [H2O] H20 H+ + OH- Keq=1.8 X 10-16 M [H2O] = 55.5 M [H2O] Keq = [H+ ] [OH- ] (1.8 X 10-16 M)(55.5 M ) = [H+ ] [OH- ] 1.0 X 10-14 M2 = [H+ ] [OH- ] = Kw If [H+ ]=[OH- ] then [H+ ] = 1.0 X 10-7
  • 15. pH Scale  Devised by Sorenson (1902)  [H+] can range from 1M and 1 X 10-14 M  using a log scale simplifies notation  pH = -log [H+ ] Neutral pH = 7.0
  • 16. Weak Acids and Bases Equilibria •Strong acids / bases – disassociate completely •Weak acids / bases – disassociate only partially •Enzyme activity sensitive to pH • weak acid/bases play important role in protein structure/function
  • 17. Acid/conjugate base pairs HA + H2O A- + H3O+ HA A- + H+ HA = acid ( donates H+ )(Bronstad Acid) A- = Conjugate base (accepts H+ )(Bronstad Base) Ka = [H+ ][A- ] [HA] Ka & pKa value describe tendency to loose H+ large Ka = stronger acid small Ka = weaker acid pKa = - log Ka
  • 18. pKa values determined by titration
  • 19. Phosphate has three ionizable H+ and three pKas
  • 20. Buffers • Buffers are aqueous systems that resist changes in pH when small amounts of a strong acid or base are added. • A buffered system consist of a weak acid and its conjugate base. • The most effective buffering occurs at the region of minimum slope on a titration curve (i.e. around the pKa). • Buffers are effective at pHs that are within +/-1 pH unit of the pKa
  • 21. Henderson-Hasselbach Equation 1) Ka = [H+ ][A- ] [HA] 2) [H+ ] = Ka [HA] [A- ] 3) -log[H+ ] = -log Ka -log [HA] [A- ] 4) -log[H+ ] = -log Ka +log [A- ] [HA] 5) pH = pKa +log [A- ] [HA] HA = weak acid A- = Conjugate base * H-H equation describes the relationship between pH, pKa and buffer concentration
  • 22. Case where 10% acetate ion 90% acetic acid • pH = pKa + log10 [0.1 ] ¯¯¯¯¯¯¯¯¯¯ [0.9] • pH = 4.76 + (-0.95) • pH = 3.81
  • 23. • pH = pKa + log10 [0.5 ] ¯¯¯¯¯¯¯¯¯¯ [0.5] • pH = 4.76 + 0 • pH = 4.76 = pKa Case where 50% acetate ion 50% acetic acid
  • 24. • pH = pKa + log10 [0.9 ] ¯¯¯¯¯¯¯¯¯¯ [0.1] • pH = 4.76 + 0.95 • pH = 5.71 Case where 90% acetate ion 10% acetic acid
  • 25. • pH = pKa + log10 [0.99 ] ¯¯¯¯¯¯¯¯¯¯ [0.01] • pH = 4.76 + 2.00 • pH = 6.76 • pH = pKa + log10 [0.01 ] ¯¯¯¯¯¯¯¯¯ [0.99] • pH = 4.76 - 2.00 • pH = 2.76 Cases when buffering fails